CN113105584B - Castor oil-based reprocessable thermosetting elastomer and preparation method thereof - Google Patents
Castor oil-based reprocessable thermosetting elastomer and preparation method thereof Download PDFInfo
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- 239000004359 castor oil Substances 0.000 title claims abstract description 85
- 235000019438 castor oil Nutrition 0.000 title claims abstract description 85
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 title claims abstract description 85
- 229920001971 elastomer Polymers 0.000 title claims abstract description 59
- 239000000806 elastomer Substances 0.000 title claims abstract description 59
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000178 monomer Substances 0.000 claims description 38
- 150000001336 alkenes Chemical class 0.000 claims description 33
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 33
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 31
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 14
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 230000001681 protective effect Effects 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 150000004985 diamines Chemical class 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 3
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims 1
- 239000012895 dilution Substances 0.000 claims 1
- 238000004090 dissolution Methods 0.000 claims 1
- 150000004662 dithiols Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 28
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 238000004132 cross linking Methods 0.000 description 14
- 239000007789 gas Substances 0.000 description 9
- 238000012958 reprocessing Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 229920006037 cross link polymer Polymers 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- XLGSEOAVLVTJDH-UHFFFAOYSA-N 12-(1-adamantylcarbamoylamino)dodecanoic acid Chemical compound C1C(C2)CC3CC2CC1(NC(=O)NCCCCCCCCCCCC(=O)O)C3 XLGSEOAVLVTJDH-UHFFFAOYSA-N 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000011243 crosslinked material Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- SZZDTLAYEZVLPG-UHFFFAOYSA-N o-(5-aminopentyl)hydroxylamine Chemical compound NCCCCCON SZZDTLAYEZVLPG-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- IUNKMGFWTJFRNY-UHFFFAOYSA-N butoxymethanedithiol Chemical compound CCCCOC(S)S IUNKMGFWTJFRNY-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- FAFWKDXOUWXCDP-UHFFFAOYSA-N ethenylurea Chemical compound NC(=O)NC=C FAFWKDXOUWXCDP-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- JBPWRHDFVVEDTJ-UHFFFAOYSA-N oxadithiole Chemical compound O1SSC=C1 JBPWRHDFVVEDTJ-UHFFFAOYSA-N 0.000 description 1
- 239000011846 petroleum-based material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/36—Amides or imides
- C08F222/38—Amides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2335/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
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Abstract
The invention discloses a castor oil based reworkable thermosetting elastomer, which relates to the technical field of high polymer materials, and has the following structural formula:
wherein x is more than or equal to 1 and less than or equal to 50, y is more than or equal to 3 and less than or equal to 50, and z is more than or equal to 5 and less than or equal to 5000. The invention also provides a preparation method of the reworkable thermosetting elastomer. The invention has the beneficial effects that: the elastomer of the invention can be reprocessed, and the performance of the material is not obviously reduced after repeated use, and the material has good elasticity due to the existence of the cross-linked network.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a castor oil based reworkable thermosetting elastomer and a preparation method thereof.
Background
Currently, the problems of global warming, environmental pollution, and exhaustion of fossil energy resources are becoming more severe. In 2019, the national government committees Zhao Yiwu suggest to develop the bio-based material, so that the problem of white pollution can be fundamentally solved, the consumption of the material industry on petroleum can be greatly reduced, and the pressure of petrochemical resources is relieved.
The united nations environmental agency reports that the pollution disaster caused by non-degradable plastic materials from petroleum has spread to every corner of the world, and the number of plastic bags used worldwide is as many as 5 trillion every year. However, only 9% of the 90 million tons of plastics produced in the world to date have been recycled, with the remainder being mostly thrown into landfills, or the natural environment. Therefore, in order to solve the problems of non-recyclability and non-recyclability of such materials, a search for bio-based reworkable materials is necessary.
It is readily apparent that petroleum-based plastics pose challenges to the environment and human health, and it is currently difficult to replace them with sustainable bio-based plastics that have similar mechanical properties. The addition of small, uniformly oriented filler particles to polymers can improve their mechanical properties, but methods for controlling particle orientation in polymers have not been developed. Therefore, the search for using bio-based materials to replace petroleum-based materials is one of the global hot research directions.
The bio-based material is a new material which is manufactured by using renewable biomass as a raw material, including crops and wastes thereof, such as straws and the like, through biological, chemical, physical and other methods, and has the advantages of environmental protection, energy conservation, emission reduction, renewable raw materials and the like. The wide application and industrial development of the bio-based materials conform to the strategic requirements of sustainable development and energy conservation and emission reduction in China, and can bring new economic points and have huge development potential. For example, patent publication No. CN107501554A discloses an ultrahigh strength thermoplastic elastomer and a preparation method thereof, but at the same time, finding a bio-based material whose performance meets or exceeds the use condition, and expanding its recyclability to expand the use field of the material is an obstacle to the development of the bio-based material industry in China at present.
The thermosetting resin has the advantages of good heat resistance, high specific strength and the like, is widely applied to production and life, and causes the problems of resource waste, environmental pollution and the like due to the difficulty brought to reprocessing caused by the permanent cross-linked network structure or the great reduction of the material performance after reprocessing.
Disclosure of Invention
The invention aims to solve the technical problems that the thermosetting resin in the prior art brings difficulty to reprocessing due to the permanent cross-linked network structure of the thermosetting resin, or the performance of the material after reprocessing is greatly reduced, so that the waste of resources, the environmental pollution and the like are easily caused.
The invention solves the technical problems through the following technical means:
a castor oil based reprocessable thermoset elastomer having the structural formula:
Has the advantages that: the elastomer of the invention can be reprocessed, and the performance of the material is not obviously reduced after repeated use, and meanwhile, the material has good elasticity due to the existence of a cross-linked network, and the breaking strain is 20-1000%. Compared with the traditional crosslinking material, such as natural rubber, the tensile stress of the natural rubber is 10-30MPa, the breaking strain is 0-1000%, the material keeps the original elasticity after crosslinking, the mechanical property is improved compared with that before crosslinking, and the breaking stress is 1-50 MPa.
Preferably, said R is 1 Is any one of the following structural formulas
Preferably, said R is 2 Is any one of the following structures:
the invention also provides a preparation method of the castor oil based reworkable thermosetting elastomer, which comprises the following steps:
(1) mixing 0.1-1000 parts by weight of castor oil based elastomer with 10-10000 parts by weight of solvent, heating for dissolving, and introducing protective gas into the mixed solution for 10-60 min;
(2) dissolving 0.01-100 parts by weight of diamine in 1-1000 parts by weight of solvent, mixing the obtained solution with the mixed solution in the step (1), and then reacting at 50-100 ℃ for 8-24 h;
(3) and (3) heating the reaction product in the step (2) to form a film, and drying the film to obtain the castor oil based reworkable thermosetting elastomer.
Has the advantages that: the castor oil-based elastomer of the invention is dynamically crosslinked with diamine. The crosslinked polymer elastomer can be reprocessed, the performance of the material after repeated use is not obviously reduced, and the material has good elasticity and the breaking strain is 20-1000 percent because of the existence of the crosslinked network. Compared with the traditional cross-linked material, the material keeps the original elasticity after cross-linking, and the mechanical property is improved to a certain extent compared with that before cross-linking, and the breaking stress is 1-50 MPa.
The ratio of diamine to castor oil based elastomer is designed to be saturated, i.e. exactly fully reacted. When the amount of the diamine added is less than the above range, the degree of crosslinking is low, and thermosetting of the material cannot be exhibited. When the reaction temperature is 20 ℃, the reaction cannot occur.
Preferably, the solvent in step (1) and step (2) is DMF, toluene, chlorobenzene or DMSO.
Preferably, the diamine in step (2) is 1, 6-hexanediamine.
Preferably, the reaction product in step (2) is dried at 50-100 ℃ for 8-48 h.
Preferably, the preparation method of the castor oil-based elastomer comprises the following steps:
(1) 1-100 parts by weight of castor oil-based olefin monomer 1, 1-100 parts by weight of castor oil-based olefin monomer 2, 1-100 parts by weight of castor oil-based olefin monomer 3, 1-100 parts by weight of oxahexanedithiol and 10 -1 -10 parts by weight of catalyst are placed in a reaction vessel and 1-10000 parts by weight of solvent are added;
(2) introducing protective gas into the reactant in the step (1) for 1-30min, and reacting at 50-100 ℃ for 8-24 h;
(3) and (3) adding the reactant into a solvent with the same amount as that in the step (1) to dilute and dissolve, purifying with methanol, and drying to obtain the castor oil-based elastomer.
Has the advantages that: castor oil-based olefin monomer and oxadithiol are utilized to obtain castor oil-based elastomer through free radical polymerization, a dynamic covalent bond is introduced into a polymer side group, and the polymer can be dynamically crosslinked with diamine under the heating condition.
Preferably, the structural formula of the castor oil-based olefin monomer 1 is as follows:
the structural formula of the castor oil-based olefin monomer 2 is as follows:
the structural formula of the castor oil-based olefin monomer 3 is as follows:
preferably, the solvent is THF and the catalyst is AIBN.
The invention has the advantages that: the elastomer can be reprocessed, the performance of the material is not obviously reduced after repeated use, and the material has good elasticity and the breaking strain is 20-1000 percent because of the existence of the cross-linked network. Compared with the traditional cross-linked material, the material keeps the original elasticity after cross-linking, and the mechanical property is improved to a certain extent compared with that before cross-linking, and the breaking stress is 1-50 MPa.
Drawings
FIG. 1 is a flow chart of the preparation of castor oil based olefin monomer 2 according to example 1 of the present invention;
FIG. 2 is a flow chart of the preparation of castor oil based elastomer according to example 2 of the present invention;
FIG. 3 is a flow chart of the preparation of castor oil based reworkable thermoset elastomer according to example 3 of the present invention;
FIG. 4 is a nuclear magnetic hydrogen spectrum of castor oil based olefin monomer in examples 1 and 2 of the present invention;
FIG. 5 is a stress-strain plot of castor oil-based elastomer of example 2 of the present invention;
fig. 6 is a stress-strain plot of castor oil-based reworkable thermoset elastomer of example 3 of the present invention.
Fig. 7 stress-strain diagram of recycling and reprocessing of castor oil-based reworkable thermosetting elastomer according to example 3 of the present invention for 3 times.
Fig. 8 is a stress relaxation graph of castor oil-based reworkable thermoset elastomer of example 3 of the present invention.
FIG. 9 shows a nuclear magnetic resonance hydrogen spectrum of comparative example 1 of the present invention.
Fig. 10 is a stress-strain plot of castor oil-based reworkable thermoset elastomer of example 5 of the present invention.
Fig. 11 is a stress-strain plot of castor oil-based reworkable thermoset elastomer of example 6 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
Example 1
The preparation method of the castor oil-based olefin monomer 2 has a preparation flow chart shown in figure 1 and specifically comprises the following steps:
(1) taking 10 parts by weight of castor oil based olefin monomer 1(UDA), 0.1 part by weight of Dimethylaminopyridine (DMAP) and dissolving in 1000 parts by weight of tetrahydrofuran, and introducing protective gas for 30min, wherein the structural formula of the castor oil based olefin monomer 1 in the embodiment is as follows:
(2) 12 parts by weight of diketene was dissolved in 100 parts by weight of a tetrahydrofuran solution, and then added to the flask of step (1), the flask was sealed, and reacted at 60 ℃ for 24 hours. The reaction was extracted with dichloromethane and washed with saturated brine to obtain ricinoleic olefin monomer 2 (DKUDA).
Example 2
The preparation method of the castor oil-based elastomer has a preparation flow chart shown in figure 2 and specifically comprises the following steps:
(1) mixing 40 parts by weight of castor oil-based olefin monomer 1(UDA), 15 parts by weight of castor oil-based olefin monomer 2(DKUDA) and 45 parts by weight of castor oil-based olefin monomer 3(AUDA), adding 100 parts by weight of oxydiol, adding 1000 parts by weight of THF, placing in a flask, introducing protective gas into the mixed solution for 30min, and heating to dissolve;
(2) 5 parts by weight of AIBN was dissolved in 10 parts by weight of THF and then charged into the flask of step (1) and reacted at a reaction temperature of 65 ℃ for 24 hours. And purifying the reactant in methanol to obtain the castor oil-based elastomer.
The structural formula of the castor oil based olefin monomer 3(AUDA) in this example is as follows:
Example 3
The preparation method of the castor oil based reworkable thermosetting elastomer has a preparation flow chart shown in figure 3, and specifically comprises the following steps:
(1) mixing 5 parts by weight of the castor oil-based elastomer prepared in the example 2 with 80DMF (dimethyl formamide), heating to dissolve the castor oil-based elastomer, and introducing protective gas into the mixed solution for 30 min;
(2) dissolving 1 part of 1, 6-hexamethylene diamine in 40 parts of DMF, adding the obtained solution into the flask in the step (1), and reacting at 80 ℃ for 24 hours;
(3) pouring the reaction product in the step (2) into polytetrafluoroethylene, and heating for 24 hours at the temperature of 80 ℃ on a heating table until a film is formed;
(4) and (4) drying the product obtained in the step (3) in an oven at the temperature of 80 ℃ to obtain the castor oil based reworkable thermosetting elastomer.
Example 4
The preparation method of the castor oil based reworkable thermosetting elastomer specifically comprises the following steps:
(1) mixing 5 parts by weight of the castor oil-based elastomer prepared in the example 2 with 80 parts by weight of DMF, heating to dissolve the mixture, and introducing protective gas into the mixed solution for 30 min;
(2)0.1 part by weight of 1, 6-hexamethylenediamine was dissolved in 40 parts of DMF, and the resulting solution was added to the flask in step (1) and reacted at 80 ℃ for 24 hours;
(3) pouring the reaction product in the step (2) into polytetrafluoroethylene, and heating for 12 hours at the temperature of 80 ℃ on a heating table until a film is formed;
(4) and (4) drying the product obtained in the step (3) in an oven at the temperature of 80 ℃ to obtain the castor oil based reworkable thermosetting elastomer 1.
Example 5
The preparation method of the castor oil based reworkable thermosetting elastomer specifically comprises the following steps:
(1) mixing 0.1 part by weight of the castor oil-based elastomer prepared in the example 2 with 10000 parts by weight of DMF (dimethyl formamide), heating to dissolve the mixture, and introducing protective gas into the mixed solution for 30 min;
(2) dissolving 100 parts by weight of 1, 6-hexamethylenediamine in 1 part by weight of DMF, adding the obtained solution into the flask in the step (1), and reacting at 100 ℃ for 8 hours;
(3) pouring the reaction product in the step (2) into polytetrafluoroethylene, and heating at 80 ℃ for 12h until a film is formed;
(4) And (4) drying the product obtained in the step (3) in an oven at the temperature of 80 ℃ to obtain the castor oil based reworkable thermosetting elastomer 2.
Example 6
The preparation method of the castor oil based reworkable thermosetting elastomer comprises the following steps:
(1) mixing 1 part by weight of the castor oil-based elastomer prepared in the example 2 with 100 parts by weight of DMF (dimethyl formamide), heating to dissolve the mixture, and introducing protective gas into the mixed solution for 30 min;
(2)0.2 part by weight of oxa 1, 6-hexanediamine was dissolved in 10 parts by weight of DMF, and the resulting solution was charged into the flask in the step (1) and reacted at 80 ℃ for 24 hours; wherein the structural formula of the oxa 1, 6-hexanediamine is as follows:
(3) pouring the reaction product in the step (2) into polytetrafluoroethylene, and heating at 80 ℃ for 12h until a film is formed;
(4) and (4) drying the product obtained in the step (3) in an oven at the temperature of 80 ℃ to obtain the castor oil based reworkable thermosetting elastomer 3.
Experimental data and analysis:
fig. 4 is nuclear magnetic hydrogen spectra of the castor oil based olefin monomer 1, the castor oil based olefin monomer 2 and the castor oil based olefin monomer 3 in example 1 and example 2, and it can be seen from the figures that all the characteristic peaks of the monomers obtained according to the preparation route successfully appear, and no hetero-peak exists, which indicates that the purity of the prepared monomers is very high.
Fig. 5 is a stress-strain curve diagram of the castor oil-based elastomer, and it can be seen that the breaking strain of the castor oil-based elastomer can reach 20MPa, and the breaking stress can reach 560%.
The castor oil-based reworkable thermoset elastomer of example 3 was reworked for testing
The test method is as follows:
(1) 600mg of the castor oil base obtained in the above example 3 was used as a reprocessable thermosetting elastomer, and the film was formed by vacuum molding for 20min at a temperature of 170 ℃ and a pressure of 10MPa with a vacuum film press.
(2) Cutting the film prepared in the step (1) into dumbbell-shaped sample strips by using a cutter, and performing tensile test by using a universal mechanical testing machine, wherein the tensile speed is set to be 10 mm/min.
(3) And (3) cutting the film subjected to the tensile test in the step (2) into pieces, and tabletting. And (3) tabletting conditions are the same as those in the step (1), and then mechanical property test is carried out to obtain the performance of the sample recovered for 1 time.
(4) The multiple recovery test method is the same as the above steps. FIG. 6 is a stress-strain plot of castor oil based reworkable thermoset elastomers showing strain at break up to 30MPa and stress at break of about 600%. The stress was increased by 50% compared to before crosslinking.
Fig. 7 is a stress-strain curve diagram of reprocessing of the castor oil-based reworkable thermosetting elastomer, and it can be seen that the performance of the sample does not change much for a plurality of times of processing of the sample, and a good repeating effect is obtained.
Fig. 8 is a graph of the stress relaxation curves of example 3 castor oil based reworkable thermoset elastomers at different temperatures. Stress relaxation is a characteristic feature of crosslinked polymers, and thus this elastomer can be proved to be a thermosetting crosslinked polymer.
Comparative example 1
(1) 1 part by weight of castor oil based olefin monomer 2(DKUDA) was taken and placed in a flask, and 80 parts by weight of DMF was added to dissolve it, and a shielding gas was introduced.
(2) 1.05 parts of 1, 6-hexanediamine is dissolved in 20 parts of DMF and added to the round-bottomed flask described in step (1), and the reaction is stirred at 80 ℃ for 24 hours.
(3) And (3) placing the reactant obtained in the step (2) in an oven to remove the solvent, and drying to obtain the model polymer. The nuclear magnetic numbers before and after crosslinking are shown in FIG. 8.
Fig. 9 is a nuclear magnetic hydrogen spectrum before and after the cross-linking of the castor oil-based olefin monomer 2 and the 1, 6-hexanediamine, and it can be seen from the figure that the characteristic peaks of the crosslinked castor oil-based olefin monomer 2, 3 disappear, the characteristic peaks of the cross-linking bond appear, and the ratio of the integral areas is 96%, which indicates that the castor oil-based olefin monomer 2 and the 1, 6-hexanediamine are successfully cross-linked. The addition of diamine is proved to be accompanied with the generation of a cross-linking structure, reversible covalent bonds (vinyl urea) are generated between amino groups and 2 side groups of the castor oil-based olefin monomer, and the occurrence of the cross-linking reaction can be proved by nuclear magnetism. However, in the case of the example, the castor oil-based elastomer is reacted, the crosslinked structure cannot be verified by nuclear magnetism.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (5)
1. A castor oil based reworkable thermoset elastomer characterized by: the preparation method comprises the following steps:
(1) mixing 0.1-1000 parts by weight of castor oil based elastomer with 10-10000 parts by weight of solvent, heating for dissolving, and introducing protective gas into the mixed solution for 10-60 min;
the preparation method of the castor oil-based elastomer comprises the following steps:
1) 1-100 parts by weight of castor oil-based olefin monomer 1, 1-100 parts by weight of castor oil-based olefin monomer 2, 1-100 parts by weight of castor oil-based olefin monomer 3, 1-100 parts by weight of dithiol and 10 -1 -10 parts by weight of catalyst are placed in a reaction vessel and 1-10000 parts by weight of solvent are added;
2) introducing protective gas into the reactant of 1) for 1-30min, and reacting at 50-100 ℃ for 8-24 h;
3) Adding the reactant of the step 2) into a solvent which is equal to the solvent in the step 1) for dilution and dissolution, purifying with methanol, and drying to obtain the castor oil-based elastomer;
the structural formula of the castor oil-based olefin monomer 1 is as follows:
the structural formula of the castor oil-based olefin monomer 2 is as follows:
the structural formula of the castor oil-based olefin monomer 3 is as follows:
(2) dissolving 0.01-100 parts by weight of diamine in 1-1000 parts by weight of solvent, mixing the obtained solution with the mixed solution in the step (1), and then reacting at 50-100 ℃ for 8-24 h;
(3) and (3) heating the reaction product in the step (2) to form a film, and drying the film to obtain the castor oil based reworkable thermosetting elastomer.
2. The castor oil-based reworkable thermoset elastomer of claim 1, wherein: the solvents in the step (1) and the step (2) are DMF, toluene, chlorobenzene or DMSO.
3. The castor oil-based reworkable thermoset elastomer of claim 1, wherein: the diamine in the step (2) is 1, 6-hexamethylene diamine.
4. The castor oil-based reworkable thermoset elastomer of claim 1, wherein: and (3) drying the reaction product in the step (2) at 50-100 ℃ for 8-48 h.
5. The castor oil-based reworkable thermoset elastomer of claim 1, wherein: the solvent in the step 1) and the step 3) is THF, and the catalyst in the step 1) is AIBN.
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